Process and apparatus for hydrogenation



Jan. 8, 1924.

C. ELLIS PROCESS AND APPARATUS FOR HYDROGENATION F*led Nov. 25, 1918 3Sheets-Sheet l Jan. 8 1924. 1,480,251

c. ELLIS PROCESS AND APPARATUS FOR HYDROGENATION Filed Nov 25, 1918 3Sheets-Sheet 2 w I T:

F i l 1 f i Jan. 8 1924.

C. ELLIS Fnocsss Am) APPARATUS FOR HYDROGENATION Filed Nov. 25, 1918 3Sheets-Sheet 3 o \oaoo/ kaeao H0000 lm/finances;

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Patented Jan. 8, 1924.

UNITED STATES CARLETON ELLIS, OF MONTCLAIR, NEW JERSEY.

PROCESS AND APPARATUS FOR HYDROGENATION.

Application filed November 25, 1918.

To all whom it may concern:

Be it known that LCARLETON Ennis, a citizen of the United States ofAmerica. residin at Montclair, in the county of Essex and L tate of NewJersey, have invented cer tain new and useful Improvements in Proc essesand Apparatus for Hydrogenation, of which the following is aspecification.

This invention relates to the hydrogena' tion of oils and has es ecialreference to the a itation and circulation of the oil effected eitherwholly or partially by the hydrogen gas introduced, and comprises anovel method and apparatus, by means of which the agitation of the oilis effected in an ellicient manner.

In the art of hydrogenation of oil, va rious types of apparatus havebeen proposed. The prior processes which are based on forcing hydrogenthrough a body of oil all leave something to be desired in regard to thecirculation or mixing of the body of oil, especially when large unitsare employed. Mechanical stirring is resorted to in many cases, but isopen to the disadvantage of liability to allow leakage. Such stirring isuseful in a preliminary way, when used in stirring and mixing the oilwhile the same is being brought up to the hydrogenation temperature,when the hydrogenating receptacle is used for such'heating purposes.

According to present practice, the hydrogenation is usually carried outin vertical tanks, with or without mechanical stirrers, hydrogen beingblown/in atthe bottom. Such apparatus may be used successfully withunits of a few hundred, or even a few thousand pounds capacity, but withunits of say, ten to twenty thousand pounds or more, especially when theHow of gas through the liquid is relied upon to secure proper contactbetween the reacting components. irregular flow of the gas andconsequent ed dies tend to cause deposition of the catalyzer, or inother words. to prevent most effective contact of the gas with thecatalytic ma tcrial.

l f the lepth otlhe oil is increased in order to se r 6 large capacity,objectionably high pressures of hydrogen gas are needful. If u shallowbroad tank is employed, the trouble from pocketing is greatlyaggrarated.

Vertical tanks with conical or invertedpyrami lshupcd bottoms providedwith a hydrogen inlet located at the apex of the Serial R0. 264,005.

cone or pyramid, have the disadvantage of giving such a restricteddegree of circulation in the lower part, owing to its restrictedgross-section, as not to be entirely satisfact is much to be desired toprovide a receptacle of a capacity of, say, ten to fifteen or twentythousand pounds or more, which will be cheap, simple of construction,easily accessible, capable of exact temperature control, and above all,one in which the siren lation of the oil and movement of the catalyzer,when finely divided, follows definite paths capable of giving thegreatest hydrogen-absorbing etl'ect, without objectionable deposition ofcatalyzer on the bottom of the tank, or if the catalyzer does sodeposit, will throw it again into suspension in the oil under treatment.

The present invention seeks to achieve the foregoing desirable resultsby iving to the body of oil such a shape that t e hydrogen beingintroduced, preferably at or near the bottom of such body of oil,produces continuous curr nts in the body of oil, thereby effecting amixing of the oil and causing the catalyz'er to be more or lessuniformly distributed or disseminated in the oil. It is preferred alsoby so shaping the container, and hence the bottom of the body of theoil, that any of the catalyzer which drops out of the oil will graduallywork its way toward the hydrogen inlet, so as to again be distributed inthe body of oil.

Apparatus within the scope of my invention is illustrated in theaccompanying drawings, in which Fi 1 shows a vertical longitudinalsection 0 an apparatus coming within the scope of the invention, andFig. 2 shows a cross-section of the same, in termediate the endsthereof, and Fig. 3 shows a preferred form of hydrogen inle pipe ordistributor for use in the apparatus of the two figures referred toabove, which distributor is also suitable for use with several of theother figures described below. Fig. 4 is a cross-section of anothertank, showing a different arrangement of the heating coils. Figs. 5 and6 show respectively a cross-section and a longitudinal section ofanother form of apparatus embodied within the present invention, thisapparatus being particularly suited for continuous operation, andshowing a modified form of hydrogen inlet and also showing baffle platesarranged in such a manner as to aid the circulation and mixin of theoil. Fi 7 is a cross-section of stifi another modi cation of the ap'paratus, this figure showing a V-shaped trough with a vertical row ofheating pipes placed above the hydrogen inlet. Fig. 8 shows, partly inlongitudinal section and partly in elevation, and Fig. 9 shows invertical cross'section, another form of apparatus in which theunabsorbed gas removed from the gas exitof the oil treating vessel maybe cooled, purified, re-heated and returned to the oil treatingreceptacle. These forms of apparatus are intended to be illustrative ofthe many forms of apparatus comin within the scope of the presentinvention.

eferring more particularly to the drawin s, 1 represents a tank, whichis preferab y elongated and which may be cylindri cal as illustrated inFigs. 1 and 2, the length of the tank being preferably considerablyreater than its diameter. Thus, tanks hav ing a length equal to one andone-half times the diameter up to ten or more times the diameter may befound eflicient, depending upon the particular conditions under which itis desired to operate. The hydrogen distributing pipe is preferablylocated at or near the bottom of the tank, so that the hydrogenintroduced through the inlet pipe will rise, causing a flow of oil andcatalyzer in the direction of the arrows, as illustrated in the variousfigures. The tank may be rovided with suitable heating means in igS. 1and 2, heating coilS 2 being shown for this purpose, which coils may bearranged in such a manner as to form a sort of baflle on each side ofthe hydrogen inlet pipe, so that the oil carrying the finely dividedcatalyzer will be raised in the central portion of the tank, and willdrop down outside of the ballie shaped coils. as shown particularly inFig. 2. The hydrogen in troducing means together is represented by thenumeral 3.

4 represents a supply of hydrogen to the distributor 3. 5 represents apump through which the unabsorbed hydrogen collecting in the upper partof the tank 1, or in a dome 7, may be drawn through pipe 6, and passedby pipe 8, pipe 4 and distributor 3 into the mixture of oil andcatalyzer. Other pipe connections, such as an additional draw-0H pipe 9,or an additional drawpft' pipe 10, may be provided, also a pipe 11, anda pipe 12 for additional hydrogen supply may be provided. 13 'is thevalve in the pipe through which the oil or mixture of oil and finelydivided catalyzer maybe 1ntroduced into the tank, either at normaltemperature or in a preheated condition. 14 is a valve in the draw-ofi'pipe, by means of which the oil at the end of the operation may be drawnoff. A suitable thermometer 15 and a suitable test cock 16 may also beprovided at any suitable place in the tank,

preferably below the normal liquid level therein. The hydrogen inletdevice 3 may consist of the device illustrated in Fig. 3, namely, abranched pipe, one branch of which, 17, is straight, and one-half of thelength of this is provided with numerous small perforations, asillustrated, and the other half, 18, is bent and a portion of the lengthof this is likewise provided with numerous small perforations. Theperforations may be in the top of the distributor or if desired, thedistributor may be turned over as shown ;in Fig. 1 so that theperforations are in the bottom of this.

Fig. 4 illustrates a cross-section of a cylindrical tank of any desiredlength in which the process ma be carried out. This tank is provided wita hydrogen inlet 23, which may be a long pipe running substantially theentire length of the tank and provided both in its top and in its bottomwith a large number of small holes through which the hydrogen enters theoil. ,In the upper part of this tank and substantially above thehydrogen inlet may be located a. heating element composed of a coil 22,the number of pipes in each course of which is successively smallerworking downward so that bunch of pipes collectively acts as a battle tocause the separation to a certain extent of the oil passing to the ri htof this coil from the oil passing to the le t of this coil.

In F1 s. fi'and 6 I have shown a trough shaped ydrogenation vessel 25provided with a temperature regulating jacket 26. In a vessel of thischaracter suitable baflle plates 28 and 29 maybe provided to aid thecirculation. In these figures, I have shown a different variety of ahydrogen inlet de vice consisting essentially of an imperforatc pipe 30located close to the bottom of the battle 29 and connected by means ofshort pipes 31 with suitable short sections of perforated pipe 32, theends of which are preferably plugged. In this form of apparatus themixture of oil and catalyzer travels in the direction indicated by thearrows, and the mixture of oil and catalyzer may be introduced throughthe pipe 33, and may leave the apparatus through the pipe 34, alreadyhardened to the desired extent. Of course, in the commencement of theoperation in an apparatus such as shown in igs. 5 and 6. the oil ma bedrawn off and circulated through the apparatus, or the entire bulk ofoil in the apparatus at the commencement of the operation may be allowedto stand therein without any oil being drawn oil until a sufficientamount of hardening has bee i'efi'ected in this oil.

Iit Fig. 7 I have shown a still different modification, this consistingessentially of a trough of substantially V-shape cross-section, having ahydrogen inlet 37 at the lower end thereof, that is to say, in the apexof the V, and located substantially above this hy drogen inlet I mayprovide a vertical row of temperature regulating pipe 38, which also,-to some extent, act as baffles. The trough or tank is provided with atop 39 which may be curved, as illustrated, or flat if desired, and inthe latter case, a suitable dome would be provided at some point in thelength of the trough.

In the forms of ap aratus as described above, the unabsorbed hydrogencan be drawn ofi from the top of the tanks and used for any desiredpurpose. In Figs. 8 and 9, I have shown respectively a verticalelevation partly in section of an oil treating receptacle coming withinthe scope of the invention and a cross-section of the same. It isfrequently'desired to draw oil the hydrogen, which has escapedabsorption, and to subsequentl reintroduce this into the lower rt of t etank or hydrogenation rece tac e.

n the device shown in Figs. 8 and 9 of the drawings, 41 is a horizontalcylindrical vtank, the upper part of which is shown in longitudinalelevation and the lower part is shown in longitudinal section, 42 is acoil arranged for the admission of steam or hot oil for heating thecontents of the tank, as may be desired, and also for cooling purs bythe circulation of cold water or other cooling agent therethrough, whenthe temperature rises beyond the desired point due to exothermicreactions taking place| in the oil during the hydrogenation process.

43 is one form of an inlet pipe or distributor for hydrogen gas whichmay be in the form of a single perforated pipe as shown or preferablywhen using tan s of considerable length may be formed of a number ofpipes terminatin at different points in the bottom of the ydrogenatingtank, each terminus being equipped with a. "ose or similar device sothat the entire body of oil is thoroughly stirred by the fairly uniformintroduction of the hydrogen gas thereinto. 44 is a dome for collectingunabsorbed gases. 45 is a blow-oil pipe fitted with a valve, throughwhich the unabsorbed gas may be allowed to escape it very impure. forexample, at the commencement of the hydrogenation process, when aconsiderable quantity of steam or other impuritics may be present in thegas. 46 is a tank fittcd with an agitator. the driving pulley of whichis shown at 47: in which tank the oil and catulyzcr are mixed and arerun therefrom by thc pipe 48 into the trcating tank 41. The pipe 49leads from the top of thc domc 44 and may communicate with either one ofthe pipes 50 or by aropcr manipulation of-thc valves. 'Tbcpipc 50communicates directly with the pump 52. Thc pipe serves to conncct thepipe 49 with the licat exchanger 54, whereby the hot outlet gases heatthe incoming hydrogen. The out et from the pump 52 may communicate withthe regenerator or heat exchanger, by the pipe 53. The pipe 56 extendsto the purifiers 57, 58 and 59 and from the latter the pipe 60communicates with the regenerator 54. The pipe 100, through which thehydrogen is fed to the inlet 43, may be otherwise heated, e. g., byimmersing the same in a bath of hot oil, so that the hydrogen will enterthe oil in 41 at about the same temperature as said oil. Intermediatethe ends of the pipe 60 is a pump 61 which may be of the positivepressure type as indicated or may be a steam pump similar to that shownat 52. In place of using a steam pump, such as the pump 52, a positivepressure blower likewise may be used at that point. The regenerator 54consists of a shell or cylindrical chamber enclosing the pipe, I

or nest of pipes, or pipe coil through which the cold hydrogen from pipe60 is about to enter the treating tank 41. The hot unabsorbed hydrogenis allowed to blow through the s ace hctween this pipe and the cylmdricajacket thereby heating the gas about to enter the tank 41. Additionalpure hydrogen is admitted through pipe 63, as desired.

The purifiers are filled with suitableabsorbing agents, such as causticsoda solution or lumps of dry caustic soda or soda lime and the like. Asolution of caustic soda may be used in the tank 57, a solution ofpermanganate of potash may be in the tank 58. and the tank 59 maycontain cal cium chloride or soda lime for-drying purposes. Xconsiderable amount of water is removed from the oil by the hydrogen gasand this, together with other impurities taken up by the unabsorbedhydro on should bc climinatcd to a large cxtent be ore the unusedhydrogen is returned to the oil by the cyclic flow.

A layer of oil is placed in the tank 41, which layer may be of anydesired depth, but preferably completely covering the coils, and intothis oil the requisite amount of catalytic material. such asfinclyulividcd ickel, is introduced. or thc inixture of oil andfinely-divided catalyzcr is run into the tank from the tank 46. Thecatalyst is prefcrably very finely dividcd so that the gas circulationwill maintain the catalyst in suspension in the oil undcr treatment. Thelayer of oil may bc about two to four i'cct in thickness, in order tosccurc the best results oi the hydrogcn trcutnicnt. l ndcr thesecircumstances. a comp-.iratiwdy low hydrogen head or pressure issullicicnt to maintain thc rapid hydrogcn current through the oil sothat hydrogcnation takcs place quickly and cifcctivcly and without.difiicultics attendant on tho usc of strong pressures of hydrogen.During the first f and on its return is passed through the regcnerator54, thereby heating it up to about the requisite temperature. Thus hot,instead of cold, hydrogen enters the body of oil and this heating isespecially desirable when hydrogenating shallow layers of oil,

because hydrogen is a poor conductor of heat, and when traveling as astron current through a body of the oil may we lpass entirely throughthe oil without becoming heated snlliciently to react readily.

In all of the forms of apparatus illustrated and above described thecurrent of hydrogen entering near the bottom of the body of oil producesan eflicient circulation or mixing, and the catalyzer, which ispreferably finely divided, is maintained in sus pension in the oil. Anycatalyzer which may settle out of the oil during this circulation tendsto fall onto the bottom of the receptacle and works its way toward thehydrogen inlet to be again brought into susension in the body of oilunder treatment, iiy the hydrogen gas introduced.

In all of the forms of apparatus illustratedthe heating elements orcoils may be used in the commencement of the operation for heating theoil to the desired temperature, say, about 180 (1., and thereafter theheating agent to the heatin coils or elements may be cut off, and susequently the temperature of the oil may rise somewhat, due to theexothermic reaction takin place between the hydrogen and the oil.coordingly, it will be advisable during the later stage of theoperation, in order to prevent injury to the oil by overheating to passa cooling agent through the said coils or jackets.

It will be understood that the present invention is suitable for usewith cats] zers, which can be suspended in the oil, an this, of course,includes colloidal catalyzer, as well as catalyzer in the form of grainsof larger size. lVhen using a colloidal catalyzer, it is possible toemploy flat bottomed tanks or treating receptacles, since under theseconditions the catalyzer will remain suspended in the oil almostindefinitely.

The present application is in part a continuation of matter described inmy copending application No. 5,769 filed February 2, 1916 (now Patent 0.1,294,068, February 11, 1919).

I claim:

1. In the hydrogenation of fatty oils con taining unsaturatedconstituents, the step of maintaining an elongated substantiallyhoricatalyst which carried about in the oil by currents of the oi1,andintroducing thereinto, at a level well below the surface of such oil, ata plurality of points in the length of such body, a liydrogen-wutaininggas, while such oil is at a temperature at which such catalyst iscapable of causing a u iion of hydrogen with constituents of such 01 2..A process of hydrogenating oil which comprises introducing hydrogen atnear the bottom of an elongated body of oil in which are placed bailieelements so arranged, as to cause a definite circulation of the oil pastthe hydrogen inlet, such oil carrying a loose pulverulent catalyzermaintained in suspension by currents produced in said oil, such bafllealso being internally heated to heat the oil and to maintain thetemperature necessary for the hydrogenation o ration.

3. In the hydrogenation of atty oils containing unsaturatedconstituents, the step of introducing hydrogen near the bottom of ahorizontally elongated body of oil containin catalyst in suspension,such body of oil being substantiall tical movement t erein, the sides ofsuch body of oil sloping toward the hydrogen inlet, whereby any of thecatalyst which may settle out tends to work its Waytoward the saidhydrogen inlet, and thereby bringingany catalyst which settles out ofsaid oil back to positions near said hydrogen inlets, whereby the sametends to be again thrown into suspension in the said oil.

4. A process which comprises introducing hydrogen at a row of pointslrwated near the bottom of an elongated body of fatty oils, in which arelocated battle elements so arranged as to cause a definite circulationof the oil past the hydrogen inlet, such oil carrying a loosepulverulent catalyzer main tained in suspension in the oil, by currentsof the oilproduced by such introduction of hydrogen, the baflle and therow of points (if introduction of the hydrogen both being substantiallyparallel to the longitudinal axis of the body of oil under treatment,and maintaining the oil at the temperature necessary for hydrogenation.

5. An apparatus for hardening fatty oils and the like comprising asubstantially horizontally arranged cylindrical receptacle adapted tocontain oil and catalyzer, means for forcing a current ofhydrogencontaining gas into the cylinder near the bottom andsubstantially beneath and parallel with the axis of the cylinder,temperature regulating coils within the cylinder spaced to either sideof the axis of the cylunobstructed as to ver-,

indar and also spaced away from the side Wllll thereof, w ereby, whenhydrogen is forced through a body of oil deep enough to cover said00115, the gas passes substantially upwardly in the oil through thespace between the coils and causes the oil and catalyzer to moveupwardly with the hydrogen and then downwardly substantially along thesidesof the cylinder to the bottom thereof.

6. An apparatus for hydrogenation comprising an elongated tank aperforated hydrogen inlet conduit located well below the normal liquidlevel and extending lengthwise of the tank, a pair of tern )eratureregulating coils located one on one side of said inlet conduit andspaced apart to leave a substantially vertical substantially freepassage in said tank, said vertical passage being in the same verticalplane with said hydrogen inlet conduit, an oil inlet and an oil outletto said tank, an outlet for unabsorbed hydro 11 located above the normaloil level in t e tank, and substantially free passages ml is providedfor the oil to pass upwardly in the passa e between the coils,horiz0ntally outwardly above the spaces occupied by the said coils,downwardl in the free passages outside said coils and inwardly towardthe plane of the said hydrogen inlet in the free passages below thespaces occupied by the said coils.

i. A horizontally arranged tank, a hydrogen inlet comprising a pluralityof hydro en inlet openings arranged substantialy lengthwise of saidtank, a pair of heatingl coils spaced apart and located one on see sideof the line of said hydrogen inlet 0 enings, said coils being spacedaway from t e walls of the tank on all sides and being located entirelybelow the normal liquid level in the tank.

8. An apparatus for hydrogenation comprisin a horizontally arrangedtank, a perforat hydrogen inlet extending lengthwise thereof andarranged in the lower part ,thereof, a hydrogen outlet connected to theupper part of said tank, a chemical purifying apparatus a heatexchanger, and

means for carryin a flow of gas from the said hydrogen outEet throughone section of the heat exchanger, through the purif ing apparatus,through the other section 0 the heat exchanger and back to the saidhydrogen inlet and a connection for bringing further amounts of hydrogeninto the cyclic gas path.

9. An apparatus for hydrogeneting oil comprising a receptacle fortreatingoi the rcatest dimension of such receptacle being horizontal,such vessel hein provided wit an inlet communicating with a. source ofoil. to be treated, a hydrogen supply device located in the lower partof said tank, and provided with inlet openings throughout at cast themajor part of the length of said treatin tank, and a verticallyextending baille rranged in said tank.

10. In the hydrogenation of fatty oils containing unsaturatedconstituents, the step of introducing hydrogen near the bottom of ahorizontally elongated body of oil containing a catalyst in suspension,such body of oil being substantially unobstructed as to verticalmovement thereln, and, by the circulation of the oil, bringing anycatalyst which settles out of said oil back into position near the pointof entry of the hydrogen gas, whereby the catalyst which settles out ofthe oil tends to be again thrown into suspension in the said oil.

11. A horizontally arranged tank, gas inlets thereto arranged along thebottom of said tank throughout at least the greater part of the lengththereof, battles in said tank arranged lengthwise thereof and located oneither side of said gas inlets, and heating means for said tank.

12. A horizontally arranged tank, free from an such obstructing surfacestherein as woulr tend to prevent circulating currents throughsubstantially the entire body of such oil,a hydrogen inlet comprising apluralih of inlet openings arranged substantial y lengthwise of saidtank, and in the lower part thereof. and a vertically extending battleforming a heating means for s2; id tank.

In testimony whereof I aflix my signature.

CARLETON ELLIS.

